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Polyoxometalate-mediated reduction of dichromate under UV irradiation

机译:多金属氧酸盐介导的紫外线重铬酸盐还原

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Reduction of Cr(VI) into Cr(III) was examined under UV light irradiation (gamma > 320 nm) in the aerated aqueous solution of four Keggin-type polyoxometalates (POM).All the POMs were effective to initiate the Cr(VI) photoreduction,but they exhibited notably different activity,following the order of H_3PW_(12)O_(40) H_4SiW_(12)O_(40) > H_4GeW_(12)O_(40) > H_3PMo_(12)O_(40).Whereas the thermodynamics favored Cr(VI) reduction by each reduced POM,the observed order in photoactivity was not in agreement with the one expected from POM redox potentials.Instead,the relative photoactivity among four POMs was exactly the same as those observed for pho-todegradation of propan-2-ol and textile dye X3B.It was proposed that generation of the reduced-POM was the rate-determining step both for Cr(VI) reduction and for organic oxidation in water.
机译:在四种Keggin型多金属氧酸盐(POM)的充气水溶液中,在紫外光(γ> 320 nm)下检测了Cr(VI)还原为Cr(III)的过程,所有POM均有效引发了Cr(VI) H_3PW_(12)O_(40) H_4SiW_(12)O_(40)> H_4GeW_(12)O_(40)> H_3PMo_(12)O_(40)的顺序显示出显着不同的活性。尽管热力学有利于每个还原的POM还原Cr(VI),但观察到的光活性顺序与POM氧化还原电势预期的顺序不一致。相反,四个POM之间的相对光活性与对pho-有人提出还原POM的生成是Cr(VI)还原和水中有机氧化的速率决定步骤。

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